Azeotropic compositions of 1,3,3,3-tetrachloroprop-1-ene and hydrogen fluoride

ABSTRACT

Provided are azeotropic or azeotrope-like mixtures of 1,3,3,3-tetrachloroprop-1-ene (HCO-1230zd) and hydrogen fluoride. Such compositions are useful as a feed stock in the production of HFC245fa and HCFO1233zd.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of application Ser. No. 13/798,385,filed Mar. 13, 2013, now U.S. Pat. No. 9,222,177 B2 the disclosure ofwhich is hereby incorporated herein by reference.

FIELD OF THE INVENTION

The present invention pertains to azeotropic or azeotrope-likecompositions of 1,3,3,3-tetrachloroprop-1-ene (HCO-1230zd) and hydrogenfluoride (HF).

BACKGROUND OF THE INVENTION

Chlorofluorocarbon (CFC) based chemicals have been widely used inindustry in a variety of different applications including asrefrigerants, aerosol propellants, blowing agents and solvents, amongothers. However, certain CFCs are suspected of depleting the Earth'sozone layer. Accordingly, more environmentally friendly substitutes havebeen introduced as replacements for CFCs. For example,1,1,1,3,3-pentafluoropropane (HFC-245fa) is recognized as havingfavorable physical properties for certain industrial applications, suchas foam blowing agents and solvents, and therefore is consider to be agood substitute for the CFCs previously used for these applications. Theuse of certain hydrofluorocarbons, including HFC-245fa, in industrialapplications is now believed to contribute to the global warming.Accordingly, more environmentally friendly substitutes forhydrofluorocarbons are now being sought.

The compound 1-chloro-3,3,3-trifluoropropene, also known as HCFO-1233zdor simply 1233zd, is a candidate for replacing HFC-245fa in someapplications, including uses as blowing agents and solvents. 1233zd hasa Z-isomer and an E-isomer. Due to differences in the physicalproperties between these two isomers, pure 1233zd(E), pure 1233zd(Z), orcertain mixtures of the two isomers may be suitable for particularapplications as refrigerants, propellants, blowing agents, solvents, orfor other uses.

1,3,3,3-tetrachloroprop-1-ene (HCO-1230zd) is the reactant in theproduction of both 245fa and 1233zd which are well known in the art asdescribed in U.S. Pat. Nos. 5,763,706 and 6,844,475, respectively. Inthe case of 1233zd, see U.S. Patent Pub. No. 2011-0201853. Thesedocuments are hereby incorporated herein by reference,

It has now surprisingly been found that an important feed stock in theproduction of both 245fa and 1233zd, is an azeotrope or azeotrope-likemixture of 1,3,3,3-tetra-chloroprop-1-ene (HCO-1230zd) and hydrogenfluoride (HF). This mixture, once formed, may thereafter be separatedinto its component parts by extraction or distillation techniques.HCO-1230zd has a boiling point of about 145° C. and HF has a boilingpoint of about 20° C. at standard atmospheric pressure. The azeotropicor azeotrope-like compositions find use not only as reactor feeds in theproduction of 245fa and 1233zd, but they are additionally useful assolvent compositions for removing surface oxidation from metals.

SUMMARY OF THE INVENTION

The invention provides a heterogeneous azeotropic composition consistingessentially of 1,3,3,3-tetrachloroprop-1-ene (HCO-1230zd) and hydrogenfluoride (HF).

The invention further provides an azeotropic or azeotrope-likecomposition which consists essentially of from about 0.2 to about 99weight percent hydrogen fluoride and from about 99.8 to about 1 weightpercent 1,3,3,3-tetrachloroprop-1-ene (HCO-1230zd), which compositionhas a boiling point of about 0° C., at pressure of about 13.3 psia.

The invention also provides a method of forming a heterogeneousazeotropic or azeotrope-like composition which consists essentially offrom about 1 to about 99 weight percent hydrogen fluoride and from about99 to about 1 weight percent 1,3,3,3-tetra-chloroprop-1-ene(HCCO-1230zd), which composition has a boiling point of about from 0°C., at pressure of about from 13.3 psia.

The invention also provides a method of forming a heterogeneousazeotropic or azeotrope-like composition which consists essentially ofblending from about 0.2 to about 97 weight percent hydrogen fluoride andfrom about 99.8 to about 3 weight percent 1,3,3,3-tetrachloroprop-1-ene(HCO-1230zd), which composition has a boiling point of about from 0° C.,at pressure of about from 13.3 psia.

It should be appreciated by those persons having ordinary skill in theart(s) to which the present invention relates that any of the featuresdescribed herein in respect of any particular aspect and/or embodimentof the present invention can be combined with one or more of any of theother features of any other aspects and/or embodiments of the presentinvention described herein, with modifications as appropriate to ensurecompatibility of the combinations. Such combinations are considered tobe part of the present invention contemplated by this disclosure.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention as claimed. Other embodimentswill be apparent to those skilled in the art from consideration of thespecification and practice of the invention disclosed herein.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows a plot of the vapor pressures of the mixtures formed inExample 1 as measured at 0° C.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

It has surprisingly been discovered that when1,3,3,3-tetrachloroprop-1-ene (HCO-1230zd) and HF were fed to a reactor,1230zd forms azeotropic or azeotrope-like mixtures with HF. Theunreacted 1230zd/HF mixture was found in the product stream.

The thermodynamic state of a fluid is defined by its pressure,temperature, liquid composition and vapor composition. For a trueazeotropic composition, the liquid composition and vapor phase areessentially equal at a given temperature and pressure. In practicalterms this means that the components cannot be separated during a phasechange.

For the purpose of this invention, an azeotrope is a liquid mixture thatexhibits a maximum or minimum boiling point relative to the boilingpoints of surrounding mixture compositions. An azeotrope or anazeotrope-like composition is an admixture of two or more differentcomponents which, when in liquid form under given pressure, will boil ata substantially constant temperature, which temperature may be higher orlower than the boiling temperatures of the components and which willprovide a vapor composition essentially identical to the liquidcomposition undergoing boiling.

For the purpose of this invention, azeotropic compositions are definedto include azeotrope-like compositions, which means a composition thatbehaves like an azeotrope, i.e., has constant-boiling characteristics ora tendency not to fractionate upon boiling or evaporation. Thus, thecomposition of the vapor formed during boiling or evaporation is thesame as or substantially the same as the original liquid composition.Hence, during boiling or evaporation, the liquid composition, if itchanges at all, changes only to a minimal or negligible extent. This isin contrast with non-azeotrope-like compositions in which during boilingor evaporation, the liquid composition changes to a substantial degree.

Accordingly, the essential features of an azeotrope or an azeotrope-likecomposition are that at a given pressure, the boiling point of theliquid composition is fixed and that the composition of the vapor abovethe boiling composition is essentially that of the boiling liquidcomposition, i.e., essentially no fractionation of the components of theliquid composition takes place. Both the boiling point and the weightpercentages of each component of the azeotropic composition may changewhen the azeotrope or azeotrope-like liquid composition is subjected toboiling at different pressures.

Thus, an azeotrope or an azeotrope-like composition may be defined interms of the relationship that exists between its components or in termsof the compositional ranges of the components or in terms of exactweight percentages of each component of the composition characterized bya fixed boiling point at a specified pressure.

The present invention provides a composition which comprises effectiveamounts of hydrogen fluoride and 1230zd to form an azeotropic orazeotrope-like composition. By effective amount is meant an amount ofeach component which, when combined with the other component, results inthe formation of an azeotrope or azeotrope-like mixture. The inventivecompositions preferably are binary azeotropes which consist essentiallyof combinations of only hydrogen fluoride with 1230zd.

In a preferred embodiment, the inventive composition contains from about99 to about 1 weight percent HF, preferably from about 90 weight percentto about 10 weight percent and most preferably from about 70 weightpercent to about 15 weight percent. In another preferred embodiment, theinventive composition contains from about 1 to about 99 weight percent1230zd preferably from about 10 weight percent to about 90 weightpercent and most preferably from about 30 weight percent to about 85weight percent.

Preferred compositions of the present invention have a boiling point ofabout 0° C. at a pressure of about 13.3 psia. An azeotropic orazeotrope-like composition having about 39±2 weight percent HF and about61±2 weight percent 1230zd has been found to boil at about 0° C., at13.3 psia.

The following non-limiting examples serve to illustrate the invention.

Example 1

14.4 g of 1,3,3,3-tetrachloroprop-1-ene (HCO-1230zd) were combined with14.4 g of HF to form a heterogeneous azeotrope mixture. This experimentwas done at 0° C., and at 13.3 psia (by visual observation).

Example 2

Binary compositions containing solely 1,3,3,3-tetrachloroprop-1-ene(HCO-1230zd) and HF are blended to form heterogeneous azeotrope mixturesat different compositions. The vapor pressures of the mixtures aremeasured at 0° C. and the following results are noticed.

Table 1 shows the vapor pressure measurement of 1230zd and HF as afunction of composition of weight percent HF at constant temperatures ofabout 0° C. The data from Table 1 are shown in graphic form in FIG. 1.

TABLE 1 P-T-X of 1230zd/HF at T = 0° C. Wt. % HF P (psia) 0.0 0.2 5.410.2 15.8 11.3 28.4 13.1 40.3 13.3 50.1 13.3 55.7 13.0 66.1 11.7 80.710.5 92.0 8.5 100.0 7.0

These data also show that the mixture is an azeotrope since the vaporpressures of mixtures of 1230zd and HF are higher, at all indicatedblend proportions, than 1230zd and HF alone, i.e., as indicated in thefirst and last rows when HF is 0.0 wt % and 1230zd is at 100.0 wt % aswell as when 1230zd is at 0.0 wt % and HF is at 100.0 wt. %.

Example 3

The azeotropic composition of the 1230zd/HF mixture is also verified byVapor-Liquid-Liquid Equilibrium (VLLE) experiment. 14.6 g of1,1,3,3-tetrachloroprop-1-ene (HCO-1230zd) were combined with 13.2 g ofHF to form a heterogeneous mixture (visual observation) at 0° C. Thevapor compositions of the mixture were sampled at temperature of 0° C.and at pressure of 13.3 psia. The result shows that the azeotropiccomposition is about 39±2 wt % HF at 0° C.

This mixture is observed to be a heterogeneous azeotrope at atemperature of 0° C. and pressure of 13.3 psia.

As used herein, the singular forms “a”, “an” and “the” include pluralunless the context clearly dictates otherwise. Moreover, when an amount,concentration, or other value or parameter is given as either a range,preferred range, or a list of upper preferable values and lowerpreferable values, this is to be understood as specifically disclosingall ranges formed from any pair of any upper range limit or preferredvalue and any lower range limit or preferred value, regardless ofwhether ranges are separately disclosed. Where a range of numericalvalues is recited herein, unless otherwise stated, the range is intendedto include the endpoints thereof, and all integers and fractions withinthe range. It is not intended that the scope of the invention be limitedto the specific values recited when defining a range.

It should be understood that the foregoing description is onlyillustrative of the present invention. Various alternatives andmodifications can be devised by those skilled in the art withoutdeparting from the invention. Accordingly, the present invention isintended to embrace all such alternatives, modifications and variancesthat fall within the scope of the appended claims.

What is claimed is:
 1. A composition consisting of1,3,3,3-tetrachloroprop-1-ene (HCO-1230zd) and hydrogen fluoride,wherein the amount of hydrogen fluoride in the composition ranges fromabout 5.4 to about 92 weight percent and wherein the composition is aheterogeneous binary azeotrope or azeotrope-like composition.
 2. Thecomposition of claim 1, wherein the amount of hydrogen fluoride in thecomposition is 5.4 weight percent.
 3. The composition of claim 1,wherein the amount of hydrogen fluoride in the composition is 15.8weight percent.
 4. The composition of claim 1, wherein the amount ofhydrogen fluoride in the composition is 28.4 weight percent.
 5. Thecomposition of claim 1, wherein the amount of hydrogen fluoride in thecomposition is 40.3 weight percent.
 6. The composition of claim 1,wherein the amount of hydrogen fluoride in the composition is 50.1weight percent.
 7. The composition of claim 1, wherein the amount ofhydrogen fluoride in the composition is 55.7 weight percent.
 8. Thecomposition of claim 1, wherein the amount of hydrogen fluoride in thecomposition is 66.1 weight percent.
 9. The composition of claim 1,wherein the amount of hydrogen fluoride in the composition is 80.7weight percent.
 10. The composition of claim 1, wherein the amount ofhydrogen fluoride in the composition is 92.0 weight percent.
 11. Acomposition consisting of 14.4 g of 1,3,3,3-tetrachloroprop-1-ene(HCO-1230zd) and 14.4 g of HF, wherein the composition is aheterogeneous binary azeotrope or azeotrope-like composition which has aboiling point of about 0° C. at a pressure of about 13.3 psia.